Diminishing world supplies and availability of crude oil as well as sporadic regional shortfalls of gasoline for motor fuel have created considerable incentive for the development and use of alternative fuels. Ethanol is gaining wide popularity as such a fuel, particularly when mixed with gasoline to form a mixture known as gasohol. Gasohol may contain up to about 10 volume percent ethanol without modifications to presently used automobile engines being required, thereby extending the volume of motor fuel availability by a like percentage.
The primary source of the ethanol used in gasohol is derived primarily from the fermentation of mash, usually from corn. Natural fermentation is able to produce an ethanol-water product mixture containing at the most about 12 vol. % ethanol. It is therefore necessary to concentrate the ethanol by distillation which, of course, requires a great amount of energy, and, in fact, the greatest cost in production of ethanol by fermentation is the energy required to separate the ethanol from the water by distillation. A means of achieving this separation without such a great expenditure of energy would thus be extremely valuable. One, therefore, might consider the many known adsorptive separation processes known in the art for possible application to the separation of ethanol from water.
For example, it is well-known in the separation art that certain crystalline aluminosilicates can be used to separate hydrocarbon species from mixtures thereof. The separation of normal paraffins from branched chain paraffins, for example, can be accomplished by using a type A zeolite which has pore openings from 3 to about 5 Angstroms. Such a separation process is disclosed in U.S. Pat. Nos. 2,985,589 and 3,201,49l. These adsorbents allow a separation based on the physical size differences in the molecules by allowing the smaller or normal hydrocarbons to be passed into the cavities within the zeolitic adsorbent, while excluding the larger or branched chain molecules.
U.S. Pat. Nos. 3,265,750 and 3,510,423, for example, disclose processes in which large pore diameter zeolites such as the type X or type Y structured zeolites can be used to separate olefinic hydrocarbons.
In addition to separating hydrocarbon types, the type X or type Y zeolites have also been employed in processes to separate individual hydrocarbon isomers. In the process described in U.S. Pat. No. 3,114,782, for example, a particular zeolite is used as an adsorbent to separate alkyl-trisubstituted benzene; and in U.S. Pat. No. 3,668,267 a particular zeolite is used to separate specific alkyl-substituted naphthalenes. In processes described in U.S. Pat. Nos. 3,558,732, 3,686,342, and 3,997,620, adsorbents comprising particular zeolites are used to separate para-xylene from feed mixtures comprising para-xylene and at least one other xylene isomer by selectively adsorbing para-xylene over the other xylene isomers. In the last mentioned processes, the adsorbents used are para-xylene selective; para-xylene is selectively adsorbed and recovered as an extract component while the rest of the xylenes and ethylbenzenes are all relatively unadsorbed with respect to para-xylene and are recovered as raffinate components. Also, in the last mentioned processes, the adsorption and desorption may be continuously carried out in a simulated moving bed countercurrent flow system, the operating principles and sequence of which are described in U.S. Pat. No. 2,985,589.
Unfortunately, with the adsorbents of the above processes separation of ethanol from water would be out of the question because all of those adsorbents are hydrophilic, i.e. they would be selective for water over the ethanol. Thus, in using any of these adsorbents it would be necessary to extract the water which is the major component and reject the ethanol into the raffinate. Also, there would be the problem of what could be used as an effective desorbent. The separation of the desorbent, if possible, from the ethanol raffinate and water extract would be considerably more costly than the primary distillation of the alcohol from the water.
As hereinafter set forth in greater detail, it has now been discovered that certain compositions of matter have been found to be useful as a selective adsorbent for ethanol over water.